Synthesis, Characterization, and Thermolysis of Dibenzo-7-dimethylgermanorbornadiene

Abstract

The dibenzo-7-dimethylgermanorbornadiene Me 2 GeA (A = C 14 H 10 ) has been synthesized in one step by treatment of MgA·3THF with Me 2 GeCl 2 in tetrahydrofuran (−35°C ) and isolated in 69% yield. The thermolysis of Me 2 GeA in toluene leads to the effective expansion of the bicyclic framework to the dibenzo-7,8-tetramethyldigermabicyclo[2.2.2]octadiene (Me 2 Ge) 2 A, isolated in 71% yield (based on germanium). The bicyclic compounds Me 2 GeA and (Me 2 Ge) 2 A have been characterized by single-crystal X-ray diffraction studies and their structures discussed.

A “masked” source for the phosphaalkene MesP=CH2: Trapping, rearrangement, and oligomerization

“…Recently, a convenient route to “masked” phosphinidenes of type F was reported starting with the conveniently generated magnesium anthracenide, MgA·3THF . This one‐step methodology is also amenable to the preparation of “masked” digermene G …”

Magnetic-Bottle and velocity-map imaging photoelectron spectroscopy of APS− (A=C14H10 or anthracene): Electron structure, spin-orbit coupling of APS•, and dipole-bound state of APS−

“…related small molecules via anthracene elimination at mild temperatures [14][15][16][17][18][19][20]. This strategy has led to successful syntheses of novel inorganic aromatic molecules such as P 2 N 3 − [15] and HCPN 3 − [19], as well as an astrophysically interesting species HCP [19].…”

“…Although the geometries of RPA compounds have been examined by X-ray crystallography [16,[18][19][20], the intrinsic electronic structure and geometry of gasphase APS − have not been studied, though they are the key molecular properties for fundamental understanding of the bond breaking and forming in producing small molecules via anthracene elimination. Therefore, we carried out a joint NIPES [29], velocity-map imaging photoelectron spectroscopy (VMI-PES) [30], and computational study of APS − , and report our findings in this paper.…”

Sulfur monoxide thermal release from an anthracene-based precursor, spectroscopic identification, and transfer reactivity

“…Fragmentation of suitable molecular precursors presents a potential entry point to explore the synthetic chemistry for such reactive species and opens new avenues for spectroscopic characterization (9)(10)(11)(12)(13)(14)(15)(16). In the case of SO, a limited number of synthetic precursors have been reported that allow thermal transfer of SO ( Fig.…”

“…Our group has a longstanding interest in small reactive species, such as P2 (9-11), AsP (12), HCP (13), phosphinidenes (14,15), and dimethylgermylene (16), generated by mild thermal activation of suitable precursors. The driving force of anthracene (C14H10, A) expulsion for the release of highly reactive molecules and subsequent characterization and synthetic transfer has been amply capitalized on (13,14,(26)(27)(28)(29)(30)(31).…”